Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
  • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
  • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
  • C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
  • C08G63/08—Lactones or lactides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
  • C10L1/2235—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom hydroxy containing
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
  • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation

Definitions

• This invention relates to novel end-functionalized polylactones. More particularly, this invention relates to novel polylactone aromatic esters and their use in fuel compositions to prevent and control engine deposits.
• polyether amine fuel additives are well known in the art for the prevention and control of engine deposits. These polyether additives have a poly(oxyalkylene) "backbone", i.e., the polyether portion of the molecule consists of repeating oxyalkylene units.
• U.S. Patent No. 4,191,537, issued March 4, 1980 to R. A. Lewis et al. discloses a fuel composition comprising a major portion of hydrocarbons boiling in the gasoline range and from 30 to 2,000 ppm of a hydrocarbyl poly(oxyalkylene) aminocarbamate having a molecular weight from about 600 to 10,000, and at least one basic nitrogen atom.
• the hydrocarbyl poly(oxyalkylene) moiety is composed of oxyalkylene units having from 2 to 5 carbon atoms in each oxyalkylene unit.
• Poly(vinyl ether) amine fuel additives are also known in the art.
• U.S. Patent No. 5,306,314 discloses poly(vinyl ether) aminocarbamate fuel additives having a vinly ether polymer backbone consisting of repeating vinyl ether units. These compounds are taught to be useful in fuel compositions to prevent and control engine deposits.
• U.S. Patent No. 4,820,432 to Lundberg et al. discloses poly (C 5 to C 9 lactone) modified Mannich base adducts which are prepared by reacting a C 5 to C 9 lactone, an amine, an aldehyde, an N-hydroxyarylamine, and a hydrocarbyl substituted C 4 to C 10 monounsaturated dicarboxylic acid producing material, such as a polyisobutenyl succinic anhydride.
• modified Mannich base adducts may be prepared, for example, by first reacting an N-hydroxyarylamine with a hydrocarbyl substituted dicarboxylic acid producing material to form an N-hydroxyaryl hydrocarbyl substituted imide, which is subsequently reacted with an aldehyde and an amine to form an intermediate Mannich base adduct having an amino functional group capable of initiating lactone ring opening polymerization, and then reacting the intermediate Mannich base adduct with a C 5 to C 9 lactone.
• This patent further teaches that the resulting poly (C 5 to C 9 lactone) modified Mannich base adduct is useful as an oil soluble dispersant additive for fuel and lubricating oil compositions.
• the present invention provides novel fuel-soluble hydrocarbyl-substituted polylactone aromatic ester fuel additives which are useful for the prevention and control of engine deposits, particularly intake valve deposits.
• the fuel-soluble polylactone aromatic esters of the present invention have the formula:
• the present invention further provides a fuel composition comprising a major amount of hydrocarbons boiling in the gasoline or diesel range and an effective deposit-controlling amount of a polylactone aromatic ester of the present invention.
• the present invention additionally provides a fuel concentrate comprising an inert stable oleophilic organic solvent boiling in the range of from about 150°F to 400°F (about 65°C to 205°C) and from about 10 to 70 weight percent of a polylactone aromatic ester of the present invention.
• the present invention is based on the surprising discovery that certain hydrocarbyl-substituted polylactone aromatic esters provide excellent control of engine deposits, especially on intake valves, when employed as fuel additives in fuel compositions.
• the fuel additives provided by the present invention have the general formula: wherein R 1 , R 2 , R 3 , R 4 and x are as defined hereinabove.
• R 1 is a hydrocarbyl group having from 1 to about 100 carbon atoms. More preferably, R 1 is a hydrocarbyl group having about 3 to about 100 carbon atoms. In a particularly preferred embodiment of the present invention, R 1 is an alkyl group having 1 to about 100 carbon atoms or an aralkyl group having 7 to about 100 carbon atoms. More preferably, R 1 is alkyl having 1 to about 100 carbon atoms. Still more preferably, R 1 is an alkyl group containing about 3 to about 100 carbon atoms.
• R 2 is preferably an alkylene group having 4 to 5 carbon atoms. More preferably, R 2 is an alkylene group having 5 carbon atoms.
• R 3 and R 4 are each independently hydrogen, hydroxy, nitro or amino, provided that R 3 and R 4 may not both be hydrogen. More preferably, R 3 is hydroxy, nitro or amino and R 4 is hydrogen or hydroxy. Even more preferably, R 3 is hydroxy and R 4 is hydrogen, or R 3 is amino and R 4 is hydrogen or hydroxy. Most preferably, R 3 is amino and R 4 is hydrogen.
• the alkyl group of the N-alkylamino moiety preferably contains 1 to 4 carbon atoms. More preferably, the alkyl group is methyl or ethyl. For example, particularly preferred N-alkylamino groups are N-methylamino and N-ethylamino groups. Most preferably, the alkyl group is methyl.
• each alkyl group of the N,N-dialkylamino moiety preferably contains 1 to 4 carbon atoms. More preferably, each alkyl group is either methyl or ethyl.
• particularly preferred N,N-dialkylamino groups are N,N-dimethylamino, N-ethyl-N-methylamino, and N,N-diethylamino groups. Most preferably, each alkyl group is methyl.
• x is an integer from 1 to 10. More preferably, x is an integer from 1 to 5.
• a preferred group of polylactone aromatic esters are those of formula I wherein R 1 is alkyl or aralkyl having 1 to about 100 carbon atoms; R 2 is alkylene having 4 to 5 carbon atoms; R 3 is hydroxy, nitro or amino; R 4 is hydrogen or hydroxy; and x is an integer from 1 to 10.
• the hydroxy, nitro, amino, N-alkylamino or N,N-dialkylamino substituent or substituents (i.e., R 3 and R 4 ) on the aromatic moiety of the polylactone aromatic esters of this invention be situated in a meta or para position relative to the ester moiety on the aromatic ring.
• R 3 and R 4 are substituents other than hydrogen, it is also preferred that these substituents be ortho to each other on the aromatic ring, as well as meta or para to the ester moiety.
• R 4 is hydrogen, it is particularly preferred that the R 3 substituent be situated in a para position relative to the ester moiety.
• the polylactone aromatic esters of the present invention will generally have a sufficient molecular weight so as to be non-volatile at normal engine intake valve operating temperatures.
• the molecular weight of the polylactone aromatic esters of this invention will range from about 250 to about 5,000, preferably from 250 to 3,000.
• Fuel-soluble salts of the polylactone aromatic esters of the present invention are also contemplated to be useful for preventing or controlling deposits.
• such salts include alkali metal, alkaline earth metal, ammonium, substituted ammonium, and sulfonium salts.
• Preferred metal salts are the alkali metal salts, particularly the sodium and potassium salts, and the substituted ammonium salts, particularly tetraalkyl-substituted ammonium salts, such as the tetrabutylammonium salts.
• Fuel-soluble salts of the polylactone aromatic esters of the present invention can also be readily prepared for those compounds containing an amino, N -alkylamino, or N,N -dialkylamino group and such salts are contemplated to be useful for preventing or controlling engine deposits.
• Suitable salts include, for example, those obtained by protonating the amino moiety with a strong organic acid, such as an alkyl- or arylsulfonic acid.
• Preferred salts are derived from toluenesulfonic acid and methanesulfonic acid.
• hydrocarbyl refers to an organic radical primarily composed of carbon and hydrogen which may be aliphatic, alicyclic, or aromatic-substituted aliphatic (e.g. aralkyl). Such hydrocarbyl groups are generally free of aliphatic unsaturation, i.e. olefinic or acetylenic unsaturation, but may contain minor amounts of heteroatoms, such as oxygen or nitrogen, or halogens, such as chlorine.
• alkyl refers to both straight- and branched-chain alkyl groups.
• alkylene refers to straight- and branched-chain alkylene groups having at least 2 carbon atoms.
• Typical alkylene groups include, for example, ethylene (-CH 2 CH 2 -), propylene (-CH 2 CH 2 CH 2 -), isopropylene (-CH(CH 3 )CH 2 -), n-butylene (-CH 2 CH 2 CH 2 CH 2 -), sec-butylene (-CH(CH 2 CH 3 )CH 2 -), n-pentylene (-CH 2 CH 2 CH 2 CH 2 CH 2 ), and the like.
• amino refers to the group: -NH 2 .
• N -alkylamino refers to the group: -NHR a wherein R a is an alkyl group.
• N,N -dialkylamino refers to the group: -NR b R c , wherein R b and R c are alkyl groups.
• polylactone refers to a ring-opened lactone polymer having the general formula: wherein R 2 is an alkylene group of 2 to 5 carbon atoms and x is an integer from about 1 to about 25.
• lactone unit refers to one monomeric unit of a polylactone polymer. Such polylactone polymers are obtained by the ring-opening polymerization of a lactone.
• polylactone is meant to include those ring-opened compounds having only about 1 lactone unit, that is, those compounds wherein x is about 1.
• the polylactone aromatic esters of this invention may be prepared by the following general methods and procedures. It should be appreciated that where typical or preferred process conditions (e.g. reaction temperatures, times, mole ratios of reactants, solvents, pressures, etc.) are given, other process conditions may also be used unless otherwise stated. Optimum reaction conditions may vary with the particular reactants or solvents used, but such conditions can be determined by one skilled in the art by routine optimization procedures.
• the protecting group will serve to protect the functional group from undesired reactions or to block its undesired reaction with other functional groups or with the reagents used to carry out the desired chemical transformations.
• the proper choice of a protecting group for a particular functional group will be readily apparent to one skilled in the art.
• Various protecting groups and their introduction and removal are described, for example, in T. W. Greene and P. G. M. Wuts, Protective Groups in organic Synthesis, Second Edition, Wiley, New York, 1991, and references cited therein.
• a hydroxy group will preferably be protected, when necessary, as the benzyl or tert-butyldimethylsilyl ether.
• Introduction and removal of these protecting groups is well described in the art.
• Amino groups may also require protection and this may be accomplished by employing a standard amino protecting group, such as a benzyloxycarbonyl or a trifluoroacetyl group.
• a standard amino protecting group such as a benzyloxycarbonyl or a trifluoroacetyl group.
• the polylactone aromatic esters of this invention having an amino group on the aromatic moiety will generally be prepared from the corresponding nitro derivative. Accordingly, in many of the following procedures, a nitro group will serve as a protecting group for the amino moiety.
• the polylactone aromatic esters of the present invention having the formula: wherein R 1 , R 2 , R 3 , R 4 and x are as defined above, may be prepared by conventional esterification reaction conditions by reacting a polylactone having the formula: wherein R 1 , R 2 and x are as defined above, with an aromatic acyl halide having the formula: wherein R 5 and R 6 are each independently hydrogen, nitro, N,N-dialkylamino, or a suitably protected hydroxy, amino or N-alkylamino group, provided that R 5 and R 6 may not both be hydrogen, and Z is a halide, such as chloride or bromide.
• polylactone aromatic esters of the present invention contain (a) a polylactone component and (b) an aromatic acyl component.
• the polylactone component of the polylactone aromatic esters of the present invention is a hydrocarbyl-substituted lactone polymer containing about 1 to about 25 lactone units.
• the polylactone component will have a hydrocarbyl-substituted lactone unit at one end of the lactone polymer and will be terminated with a hydroxyl group at the other end of the lactone polymer.
• the polylactone component of the polylactone aromatic esters of this invention is preferably prepared by polymerizing certain lactone monomers under "living polymerization” conditions.
• the term "living polymerization” is well known in the art and refers to polymerization reactions which occur in the substantial absence of chain transfer and termination reactions. Under such conditions, the reactive end of the growing polymer is essentially stable indefinitely. Accordingly, each lactone monomer can be added sequentially to the growing polylactone chain in a controlled step-by-step manner.
• living polymerization allows polylactones to be prepared having a substantially predictable sequence of lactone units.
• the polylactone polymer may be prepared by first reacting an alcohol of the formula: R 1 -OH (III) wherein R 1 is as defined above, with a suitable lactone polymerization catalyst, such as trialkylaluminum, to form a polymerization initiator which is subsequently reacted with a lactone of the formula: wherein R 2 is as defined above, to provide the desired polylactone having the formula: wherein R 1 , R 2 and x are as defined above.
• a suitable lactone polymerization catalyst such as trialkylaluminum
• reaction sequence when employing trimethylaluminum as the polymerization catalyst, the reaction sequence may be described as follows:
• the monohydroxy alcohol compound of formula III, R 1 OH, used in the above reactions is preferably a straight- or branched-chain alkyl alcohol having 1 to about 100 carbon atoms, more preferably 3 to about 100 carbon atoms; or a straight or branched-chain aralkyl alcohol containing about 7 to about 100 carbon atoms.
• Preferred straight-chain alcohols have about 3 to about 30 carbon atoms and include, for example, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, octanol, nonanol, decanol, hexadecanol (cetyl alcohol), octadecanol (stearyl alcohol) and the like.
• Preferred branched-chain alcohols include C 3 to C 30 alcohols such as iso-propanol, sec-butanol, iso-butanol, 3,5,5,-trimethyl hexanol, and the like.
• Preferred branched-chain alcohols also include those derived from polymers of C 2 to C 6 olefins, such as alcohols derived from polypropylene and polybutene. Particularly preferred are polypropylene alcohols having 9 to about 60 carbon atoms and polybutene alcohols having 8 to about 100 carbon atoms. Alcohols derived from the alpha olefin oligomers of C 8 to C 16 alpha olefins, such as the dimer, trimer and tetramer of decene as described in U.S. Patent No. 4,045,508, issued August 30, 1977 to B. L. Cupples et al., are also useful in this invention.
• lactone polymerization catalysts include alkali and alkaline earth metal hydrides, alkoxides and alkyls; alkyl aluminum and alkyl zinc compounds; alkoxides of aluminum, titanium, zirconium and tin; yttrium and rare earth metal alkoxides; and the like.
• Preferred polymerization catalysts for use with the alcohol R 1 OH are the trialkylaluminum compounds, such as trimethylaluminum and triethylaluminum.
• the reaction of alcohol R 1 OH with the polymerization catalyst will be conducted in a substantially anhydrous inert solvent at a temperature of about -50°C to about 150°C, preferably -10°C to 50° C.
• Suitable inert solvents include benzene, toluene, dichloromethane, diethyl ether and the like.
• the reaction will be conducted under a dry inert gas atmosphere, such as nitrogen or argon, at about atmospheric or ambient pressure.
• the molar ratio of alcohol to polymerization catalyst will range from about 0.5:1 to 5:1.
• the reaction product of the alcohol R 1 OH and the polymerization catalyst such as the alcohol-catalyst adduct of formula VI, is reacted with a lactone monomer of formula IV.
• the alcohol-catalyst adduct functions as an initiator for the lactone polymerization.
• Suitable lactone monomers for use in the present invention include simple lactones containing from 3 to 6 carbon atoms, such as ⁇ -propiolactone, ⁇ -methyl- ⁇ -propiolactone, ⁇ -methyl- ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, and the like.
• Preferred lactone monomers include ⁇ -valerolactone and ⁇ -caprolactone.
• An especially preferred lactone monomer is ⁇ -caprolactone.
• the living polymerization reaction will be conducted in a substantially anhydrous inert solvent which may be the same or different than the solvent employed in forming the polymerization initiator.
• the polymerization reaction temperature will generally be in the range of about -50°C to 150°C, preferably from about -10°C to 50°C.
• the polymerization reaction will be carried out under a dry, inert gas atmosphere, such as nitrogen or argon, at about atmospheric or ambient pressure.
• the molar ratio of lactone monomer to the polymerization initiator, such as the adduct of formula VI, will generally range from about 1:1 to 25:1, preferably from about 1:1 to 10:1, and more preferably from about 1:1 to 5:1.
• the time employed for the polymerization reaction can vary over a wide range and will depend to some extent on the reaction temperature and on the lactone monomers used in the polymerization process. Generally, the reaction will be conducted for about 0.05 to about 20 hours, preferably 0.05 to 1.0 hour or until essentially all the lactone monomers have reacted to form polymer.
• the reactive terminal end of the polymer is quenched by contacting the reaction mixture with about 1 to about 100 equivalents of an aqueous acid solution, such as aqueous hydrochloric acid. This affords a hydroxy-terminated polylactone of formula V.
• the hydroxy-terminated polylactone of formula V may then be coupled with a suitable aromatic acyl component using an appropriate aromatic acyl halide as described in further detail below.
• Acyl halides of formula VII may be prepared from the corresponding aromatic carboxylic acids by first protecting the hydroxy or amino groups as necessary to form a carboxylic acid having the formula: wherein R 5 and R 6 are as defined above.
• aromatic carboxylic acids which are first protected and then converted to the corresponding acyl halide are either known compounds or can be prepared from known compounds by conventional procedures.
• Representative aromatic carboxylic acids suitable for use as starting materials include, for example, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, 3-hydroxy-4-nitrobenzoic acid, 4-hydroxy-3-nitrobenzoic acid, 2-aminobenzoic acid (anthranilic acid), 3-aminobenzoic acid, 4-aminobenzoic acid, 3-amino-4-hydroxybenzoic acid, 4-amino-3-hydroxybenzoic acid, 3-( N -methylamino)benzoic acid, 4-( N -methylamino)benzoic acid, 3-( N -ethylamino)benzoic acid, 4-( N -ethylamino)benzoic acid, 3-( N
• Preferred aromatic carboxylic acids include 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, 3-hydroxy-4-nitrobenzoic acid, 4-hydroxy-3-nitrobenzoic acid, 3-aminobenzoic acid, 4'-aminobenzoic acid, 3-amino-4-hydroxybenzoic acid, and 4-amino-3-hydroxybenzoic acid.
• Particularly preferred aromatic carboxylic acids include 4-aminobenzoic acid, 4-hydroxybenzoic acid and 4-amino-3-hydroxybenzoic acid.
• the aromatic carboxylic acid contains a hydroxy group
• a hydroxy group for example, 4-hydroxybenzoic acid
• protection of the aromatic hydroxy groups may be accomplished using well-known procedures.
• the choice of a suitable protecting group for a particular hydroxy aromatic carboxylic acid will be apparent to those skilled in the art.
• Various protecting groups, and their introduction and removal, are described, for example, in T. W. Greene and P. G. M. Wuts, Protective Groups in organic Synthesis, Second Edition, Wiley, New York, 1991, and references cited therein.
• Deprotection of the aromatic hydroxy group(s) can also be accomplished using conventional procedures. Appropriate conditions for this deprotection step will depend upon the protecting group(s) utilized in the synthesis and will be readily apparent to those skilled in the art.
• benzyl protecting groups may be removed by hydrogenolysis under 1 to about 4 atmospheres of hydrogen in the presence of a catalyst, such as palladium on carbon.
• this deprotection reaction is conducted in an inert solvent, preferably a mixture of ethyl acetate and acetic acid, at a temperature of from about 0°C to about 40°C for about 1 to about 24 hours.
• Aromatic nitro groups may be reduced to amino groups using a number of procedures that are well known in the art. For example, aromatic nitro groups may be reduced under catalytic hydrogenation conditions; or by using a reducing metal, such as zinc, tin, iron, and the like, in the presence of an acid, such as dilute hydrochloric acid.
• reaction is conducted using about 1 to 4 atmospheres of hydrogen and a platinum or palladium catalyst, such as palladium on carbon.
• the reaction is typically carried out at a temperature of about 0°C to about 100°C for about 1 to 24 hours in an inert solvent, such as ethanol, ethyl acetate, toluene, and the like.
• an inert solvent such as ethanol, ethyl acetate, toluene, and the like.
• Hydrogenation of aromatic nitro groups is discussed in further detail in, for example, P. N. Rylander, Catalytic Hydrogenation in organic Synthesis, pp. 113-137, Academic Press (1979); and organic Synthesis, Collective Vol. I, Second Edition, pp. 240-241, John Wiley & Sons, Inc. (1941); and references cited therein.
• the acyl halide of formula VII may then be prepared by reacting the protected aromatic carboxylic acid with an inorganic halide, such as thionyl chloride, phosphorous trichloride, phosphorous tribromide, or phosphorous pentachloride; or with oxalyl chloride, using conventional procedures.
• an inorganic halide such as thionyl chloride, phosphorous trichloride, phosphorous tribromide, or phosphorous pentachloride; or with oxalyl chloride, using conventional procedures.
• this reaction will be conducted using about 1 to 5 molar equivalents of the inorganic acyl halide or oxalyl chloride, either neat or in an inert solvent, such as diethyl ether, at a temperature in the range of about 20°C to about 80°C for about 1 to about 48 hours.
• a catalyst such as N,N -dimethylformamide, may also be used in this reaction.
• this reaction is conducted by contacting a polylactone of formula V with about 1.0 to about 3.5 molar equivalents of an acyl halide of formula VII in an inert solvent, such as toluene, dichloromethane, diethyl ether, and the like, at a temperature in the range of about 25°C to about 150°C.
• the reaction is generally complete in about 0.5 to about 48 hours.
• the reaction is conducted in the presence of a sufficient amount of an amine base capable of neutralizing the acid generated during the reaction, such as triethylamine, di(isopropyl)ethylamine, pyridine, or 4-dimethylamino-pyridine.
• the polylactone aromatic esters of the present invention are useful as additives in hydrocarbon fuels to prevent and control engine deposits, particularly intake valve deposits.
• the desired deposit control will be achieved by operating an internal combustion engine with a fuel composition containing a polylactone aromatic ester of the present invention.
• the proper concentration of additive necessary to achieve the desired deposit control varies depending upon the type of fuel employed, the type of engine, and the presence of other fuel additives.
• the concentration of the polylactone aromatic esters of this invention in hydrocarbon fuel will range from about 50 to about 2,500 parts per million (ppm) by weight, preferably from 75 to 1,000 ppm.
• ppm parts per million
• concentrations of, for example, 30 to 70 ppm may be preferred when the present additives are employed as carburetor detergents only.
• the polylactone aromatic esters of the present invention may be formulated as a concentrate using an inert stable oleophilic (i.e., dissolves in gasoline) organic solvent boiling in the range of about 150°F to 400°F (about 65°C to 205°C).
• an aliphatic or an aromatic hydrocarbon solvent is used, such as benzene, toluene, xylene or higher-boiling aromatics or aromatic thinners.
• Aliphatic alcohols containing about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, n-butanol and the like, in combination with hydrocarbon solvents are also suitable for use with the present additives.
• the amount of the additive will generally range from about 10 to about 70 weight percent, preferably 10 to 50 weight percent, more preferably from 10 to 25 weight percent.
• additives of the present invention including, for example, oxygenates, such as t-butyl methyl ether, antiknock agents, such as methylcyclopentadienyl manganese tricarbonyl, and other dispersants/detergents, such as hydrocarbyl amines, hydrocarbyl poly(oxyalkylene) amines, or succinimides. Additionally, antioxidants, metal deactivators and demulsifiers may be present.
• oxygenates such as t-butyl methyl ether
• antiknock agents such as methylcyclopentadienyl manganese tricarbonyl
• dispersants/detergents such as hydrocarbyl amines, hydrocarbyl poly(oxyalkylene) amines, or succinimides.
• antioxidants, metal deactivators and demulsifiers may be present.
• diesel fuels other well-known additives can be employed, such as pour point depressants, flow improvers, cetane improvers, and the like.
• a fuel-soluble, nonvolatile carrier fluid or oil may also be used with the polylactone aromatic esters of this invention.
• the carrier fluid is a chemically inert hydrocarbon-soluble liquid vehicle which substantially increases the nonvolatile residue (NVR), or solvent-free liquid fraction of the fuel additive composition while not overwhelmingly contributing to octane requirement increase.
• the carrier fluid may be a natural or synthetic oil, such as mineral oil, refined petroleum oils, synthetic polyalkanes and alkenes, including hydrogenated and unhydrogenated polyalphaolefins, and synthetic polyoxyalkylene-derived oils, such as those described, for example, in U.S. Patent No. 4,191,537 to Lewis, and polyesters, such as those described, for example, in U.S. Patent Nos. 3,756,793 and 5,004,478, and in European Patent Application Nos. 356,726 and 382,159.
• carrier fluids are believed to act as a carrier for the fuel additives of the present invention and to assist in removing and retarding deposits.
• the carrier fluid may also exhibit synergistic deposit control properties when used in combination with the polylactone aromatic esters of this invention.
• the carrier fluids are typically employed in amounts ranging from about 100 to about 5,000 ppm by weight of the hydrocarbon fuel, preferably from 400 to 3,000 ppm of the fuel.
• the ratio of carrier fluid to deposit control additive will range from about 0.5:1 to about 10:1, more preferably from 2:1 to 5:1, most preferably about 4:1.
• carrier fluids When employed in a fuel concentrate, carrier fluids will generally be present in amounts ranging from about 20 to about 60 weight percent, preferably from 30 to 50 weight percent.
• Trimethylaluminum (50.0 mL of a 2.0M solution in toluene) was added to anhydrous dichloromethane (200 mL) via syringe under nitrogen. The solution was cooled to 0°C and Exxal 13 alcohol (20 grams) was added dropwise. The reaction was stirred at room temperature for 30 minutes and then cooled back to 0°C. ⁇ -Caprolactone (44.3 mL) was added all at once, the cooling bath was removed and the reaction was stirred at room temperature for sixteen hours. The reaction was quenched with 100 mL of 5% aqueous hydrochloric acid and was extracted three times with dichloromethane. The combined organic layers were dried over anhydrous magnesium sulfate, filtered and the solvents removed in vacuo to yield the desired product as a white wax.
• Trimethylaluminum (520 mL of a 2.0M solution in toluene) was added to anhydrous dichloromethane (2 L) via syringe under nitrogen. The solution was cooled to 0°C and 3,5,5-trimethylhexanol (182 mL) was added dropwise. The reaction was stirred at room temperature for 30 minutes and then cooled back to 0°C. ⁇ -Caprolactone (461 mL) was added all at once, the cooling bath was removed and the reaction was stirred at room temperature for sixteen hours. The reaction was quenched with one liter of 5% aqueous hydrochloric acid and was extracted three times with dichloromethane. The combined organic layers were dried over anhydrous magnesium sulfate, filtered and the solvents removed in vacuo to yield 596 grams of the desired product as a light yellow wax.
• Trimethylaluminum (111 mL of a 2.0M solution in toluene) was added to anhydrous dichloromethane (700 mL) via syringe under nitrogen. The solution was cooled to 0°C and polyisobutanol (210.4 grams, molecular weight average 984, prepared via hydroformylation of Amoco H-100 polyisobutene) dissolved in 800 mL of anhydrous dichloromethane was added dropwise. The reaction was stirred at room temperature for 30 minutes and then cooled back to 0°C. ⁇ -Caprolactone (49.1 mL) was added all at once, the cooling bath was removed and the reaction was stirred at room temperature for sixteen hours.
• reaction was quenched with 1 L of 5% aqueous hydrochloric acid and was extracted three times with dichloromethane. The combined organic layers were dried over anhydrous magnesium sulfate, filtered and the solvents removed in vacuo to yield 250.3 grams of the desired product as a white wax.
• test compounds were blended in gasoline and their deposit reducing capacity determined in an ASTM/CFR single-cylinder engine test.
• a Waukesha CFR single-cylinder engine was used. Each run was carried out for 15 hours, at the end of which time the intake valve was removed, washed with hexane and weighed. The previously determined weight of the clean valve was subtracted from the weight of the value at the end of the run. The differences between the two weights is the weight of the deposit. A lesser amount of deposit indicates a superior additive.
• the operating conditions of the test were as follows: water jacket temperature 200°F; vacuum of 12 in Hg, air-fuel ratio of 12, ignition spark timing of 40° BTC; engine speed is 1800 rpm; the crankcase oil is a commercial 30W oil.
• the base fuel employed in the above single-cylinder engine tests was a regular octane unleaded gasoline containing no fuel detergent.
• the test compounds were admixed with the base fuel to give a concentration of 150 ppma (parts per million actives).
• Table I illustrates the significant reduction in intake valve deposits provided by a polylactone aromatic ester of the present invention (Examples 2, 3, 5, 6 and 9) compared to the base fuel.

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Emergency Medicine (AREA)
• Combustion & Propulsion (AREA)
• Polyesters Or Polycarbonates (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=21693629

Family Applications (1)

Country Status (4)

Cited By (1)

Families Citing this family (1)

Citations (7)

• 1996
  • 1996-06-10 CA CA002178671A patent/CA2178671A1/en not_active Abandoned
  • 1996-07-01 EP EP96304859A patent/EP0752462B1/de not_active Expired - Lifetime
  • 1996-07-01 DE DE69612914T patent/DE69612914T2/de not_active Expired - Fee Related
  • 1996-07-04 JP JP8175229A patent/JPH09118743A/ja active Pending

Patent Citations (7)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events